US5707149A - Device and method for measuring the heat of reaction resulting from mixture of a plurality of reagents - Google Patents
Device and method for measuring the heat of reaction resulting from mixture of a plurality of reagents Download PDFInfo
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- US5707149A US5707149A US08/534,699 US53469995A US5707149A US 5707149 A US5707149 A US 5707149A US 53469995 A US53469995 A US 53469995A US 5707149 A US5707149 A US 5707149A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N25/00—Investigating or analyzing materials by the use of thermal means
- G01N25/20—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity
- G01N25/48—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation
- G01N25/4846—Investigating or analyzing materials by the use of thermal means by investigating the development of heat, i.e. calorimetry, e.g. by measuring specific heat, by measuring thermal conductivity on solution, sorption, or a chemical reaction not involving combustion or catalytic oxidation for a motionless, e.g. solid sample
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01K—MEASURING TEMPERATURE; MEASURING QUANTITY OF HEAT; THERMALLY-SENSITIVE ELEMENTS NOT OTHERWISE PROVIDED FOR
- G01K17/00—Measuring quantity of heat
Definitions
- the present invention relates to a device and method for measuring the heat of reaction resulting from the mixture of a plurality of liquid reagents.
- the heat of reaction is one of the most important thermochemical characteristics of any reaction and is widely used in fundamental research and applied studies, since it contains the main information on the energetics of a chemical reaction under study.
- Direct colorimetric measurements of the heats of reaction of liquid reagents are of special importance in chemistry, biochemistry, molecular biology, biotechnology, and pharmacology.
- reaction calorimetry has been limited by the relatively low sensitivity of existing instruments.
- thermochemical description of a reaction usually, for a complete thermochemical description of a reaction, one needs the knowledge of the heats of reaction across a broad range of reactant concentrations. This is achieved using special reaction calorimeters, known as titration calorimeters, which permit measurement of the heat effects upon titration of one reagent by another reagent.
- titration calorimeters special reaction calorimeters, known as titration calorimeters, which permit measurement of the heat effects upon titration of one reagent by another reagent.
- titration calorimeters that manufactured by Microcal Inc., has the ability to measure heats of reaction as small as 1 ⁇ cal. Even though the sensitivity of this instrument is much higher than that of older instruments, it is still not adequate to measure high affinity biochemical reactions.
- the main purpose of the present invention is to provide an instrument for calorimetric titration that is easier to operate, more reliable, precise, and of higher sensitivity.
- This instrument will permit a direct calorimetric determination of binding isotherms for biochemical associations with K a >10 9 M -1 .
- mixing is achieved in two stages: in the first stage a certain amount of one reagent is introduced into a certain amount of the other reagent; in the second stage, both reagents are stirred by shaking or by the action of a mechanical stirrer.
- the present invention provides a method for measuring the heat of reaction resulting from the mixture of a plurality of reagents, which method comprises the steps of providing a first liquid reagent into a compartment; providing a second reagent into the compartment so as to mix the second liquid reagent with the first reagent within the compartment; withdrawing a predetermined amount of the mixed first and second reagents from the compartment; depositing the predetermined amount of the mixed first and second reagents that has been withdrawn from the compartment back into the compartment; generating an electrical signal based on the heat of reaction of the mixed first and second reagents; and deriving data indicative of the heat of reaction based on the electrical signal.
- the present invention provides a device for measuring the heat of reaction resulting from mixture of a plurality of reagents, comprising: a compartment adapted to initially contain at least a first reagent; an injection assembly for providing a second reagent into the compartment to permit the first and second reagents to initially mix within the compartment, the injection assembly being constructed and arranged to be able to i) withdraw a predetermined portion of the first and second reagents from the compartment after the reagents have been initially mixed within the compartment and ii) deposit the withdrawn predetermined portion of the first and second reagents back into the compartment so as to facilitate stirring of the first and second reagents within the compartment; and a measuring apparatus operably connected with the compartment for deriving data indicative of the heat of reaction resulting from mixing the first and second reagents.
- FIG. 1 is a sectional front view of a calorimetric reactor in accordance with the principles of the present invention
- FIG. 2 is a sectional side view of the calorimetric reactor of the present invention.
- FIG. 3 is a sectional front view of a calorimetric reactor assembly including a reaction cell as shown in FIG. 1 in accordance with the principles of the present invention
- FIG. 4 is a sectional side view of the calorimetric reactor assembly of FIG. 3;
- FIG. 5 is a sectional side view of a dual differential calorimetric reactor assembly comprising two reactor cells in accordance with the principles of the present invention
- FIG. 6 is a schematic representation of a computer-controlled differential titration calorimeter assembly in accordance with the principles of the present invention.
- FIG. 7 is a schematic representation of a computer-controlled differential titration calorimetric assembly in accordance with the principles of the present invention in which two different types of reactors share the same thermostated block;
- FIG. 8 is a sectional front view of another embodiment of the reaction cell in accordance with the principles of the present invention.
- FIG. 9 is a sectional side view of the embodiment of the reaction cell of the present invention shown in FIG. 8;
- FIG. 10 shows the output in volts of 5 micro Joules electrical calibration pulses applied together with mixing pulses using the tween differential calorimetric cell assembly of the present invention
- FIG. 11 is a graphical representation showing the energy of the mixing pulses used in the results shown in FIG. 10;
- FIG. 12 is a graphical representation of the experimental results of the titration of pancreatic ribonuclease A (RNase) by cyclic monophosphate;
- FIG. 13 is a graphical representation of the cumulative heat of reagent binding by protein in the experimental results shown in FIG. 12.
- the present invention operates under the principle that two liquid reagents will be mixed quickly and efficiently if one of the reagents is introduced into the other with sufficient speed and turbulence. Therefore, in the present invention, the mechanical energy necessary for mixing is derived from the impulse generated by the rapid but controlled introduction of a second reagent into the calorimetric reaction cell already containing a first reagent. Stirring is accomplished either by injecting an additional amount of the first reagent or by withdrawing a portion of the mixed first and second reagents within the cell and reinjecting it into the cell. Additional stirring may be accomplished by successive withdrawal and immediate reintroduction of a small fraction of the total cell volume.
- the injected reagent or injected mixed reagents should be in the form of a high-velocity jet stream.
- the jet stream should be precisely calibrated in velocity and volume, and be directed so as to produce turbulent, circular flow in the reactor to cause the reagents to mix quickly and completely.
- the efficiency of mixing depends, in part, on the construction of the reactor--its geometry, volume, and orientation of the jet injection devices.
- the ultimate sensitivity and accuracy of the entire calorimetric instrument also depends on these elements and may also be influenced by other factors, such as the construction of the calorimeter cell or compartment, inlets and outlets to and from the cell, thermostation for maintaining the compartment at a relatively constant temperature, sensors, injection devices for the injection of reagents at the desired volume and speed, and the automatization of the measuring process.
- FIGS. 1 and 2 are schematic representations of a calorimetric reactor, generally indicated at 10, manufactured in accordance with the principles of the present invention.
- the reactor 10 includes a main compartment in the form of a thin cylindrical cell or compartment 12, made from a chemically inert metal, such as gold or stainless steel, or other material that is chemically inert and of high thermal conductivity.
- Cell 12 has circular end walls 13, as shown in FIG. 2, and a peripheral rim 15 defining its generally cylindrical shape. These end walls 13 preferably have a diameter greater than the distance therebetween.
- the cell's volume is preferably between 0.3-1.5 ml, with a typical diameter of the circular end walls 13 being approximately between 20-25 mm, and a typical distance between the circular end walls 13 being approximately 2-3 mm.
- the cell 12 has two inlet tubes, including a radial inlet tube 14 and a tangential inlet tube 16, and one outlet tube 18.
- the tubes 14, 16 and 18 are made from a chemically inert material having a relatively low thermal conductivity, such as platinum, TEFLON (polytetrafluorethylene), or stainless steel.
- the inner diameter of the tubes is preferably between about 0.5-1.0 mm.
- the tubes are welded or otherwise rigidly connected with the rim 15.
- the assembly is preferably constructed and arranged such that the circular end walls 13 are vertically disposed, the outlet tube 18 is connected at the top of the rim 15, the tangential inlet tube 16 is connected at the bottom of the rim 15, and the radial inlet tube 14 is connected at the side of the rim.
- a calibration heater (not shown) used for calibrating the instrument is also located at the rim of the cell.
- each reactor 10 is connected with an injector apparatus, generally indicated at 19, which includes a pair of injection devices 20 and 22, for introducing the two reagents into the cell 12 and for achieving high efficiency mixing of the reagents within the cell.
- injector apparatus generally indicated at 19
- inlet tubes 14 and 16 provide a conduit through which injection devices 20 and 22, respectively, are in fluid communication with the cell 12.
- the rim 15 is provided with a pair of holes 23 and 25, preferably about 0.1-0.2 mm in diameter, which permit the inlet tubes 14 and 16, respectively, to communicate with the cell 12.
- the outlet tube 18 connects the cell 12 with a drain or collection tube (shown as reference numeral 29 in FIG. 6) for disposal of the mixed reagents.
- a drain or collection tube shown as reference numeral 29 in FIG. 6
- Each injection device together with its respective inlet tube can be considered as being a single injection assembly.
- each cell or compartment 12 can be considered to be connected to a first injection assembly (e.g., 14, 20) and a second injection assembly (e.g., 16, 22) .
- Injection devices 20 and 22, as shown in FIG. 6, are capable of injecting liquid into cell 12, via inlet tubes 14 and 16, with a controlled speed and volume, and are commercially available, for example, from Hamilton Inc. (model 940). They are each in the form of an electrically operated automatic syringe assembly with a mechanical piston/cylinder arrangement that is capable of injecting and withdrawing the reagents to and from the cell 12. Injection device 20, which is connected with the radially oriented inlet tube 14, operates to shoot a jet radially towards the center of cell 12 and is used for injecting the titrating reagent into the cell.
- the injection device 22 is connected with the tangentially oriented inlet tube 16 and operates to shoot a jet generally tangentially with respect to the cell.
- the tangential injection device 22 allows repeated withdrawal and reinjection of a fraction of the total cell volume through tangential inlet tube 16 and is used for additional steering of the reagents after they are initially provided into the cell.
- the tangential disposition of tube 16 is highly preferred as it creates a turbulent, circular flow of mixed reagents in a uniform direction within the cell that causes rapid and complete mixing.
- FIGS. 3 and 4 show a calorimetric reactor assembly 27 incorporating a reactor 10 as described in conjunction with FIGS. 1 and 2. From FIGS. 3 and 4, it can be appreciated that the cell 12 is squeezed or compressed between two conventional semiconductor thermopiles, including a measuring thermopile 26 and a compensating thermopile 28, which make good thermal contact with the exterior surfaces of the opposite flat circular walls 13 of the cell.
- the thermopiles are each compressed between the cell 12 and a surrounding thermostated block 30.
- the thermostated block 30, preferably made of solid copper, makes good thermal contact with sides of the thermopiles and is maintained at a constant temperature.
- the thermostated block 30 defines a symmetrical surrounding for the cell.
- FIG. 5 shows a dual calorimeter, which includes a pair of calorimetric reactor assemblies 27 that share a common thermostated wall 31, as shown.
- the measuring thermopiles 26 in FIGS. 3-5 are used as sensors to detect the temperature difference between the respective cells 12 and the surrounding thermostated block 30.
- the compensating thermopiles 28 produce Peltier heat as part of a feedback control mechanism for compensating the heat effects arising from the mixing of the reagents, as will be described in conjunction with FIG. 6.
- Conventional semiconductor thermopiles having 64 junctions and an area of approximately 11.5 ⁇ 9.2 mm 2 are preferably used.
- FIG. 6 is a schematic view of the differential titration calorimetric assembly 100 of the present invention. From FIG. 6, it can be appreciated that the operation, sequence of jet pulses, and the duration and speed of jet pulses from injectors 20 and 22, can all be controlled by a data processor, preferably in the form of a computer 40.
- the concentration of the other reagent in the cell decreases.
- the concentration of both reagents in the cell is known at all times by the computer 40, which takes this into account during calculation of the heat of reaction.
- the heat effects are compensated by the Peltier heat produced by the compensating thermopiles 28 so as to maintain the cell 12 at a generally constant temperature throughout operation.
- the compensating Peltier heat is controlled by the computer 40 in accordance with the signals received from the measuring thermopile 26. More specifically, the measuring thermopiles 26 generate measuring signals as a function of the temperature difference between the respective cell 12 and the surrounding thermostated block. The measuring signals are amplified by amplifiers 21, as shown in FIG. 6, and received by computer 40, which in turn generates compensation signals proportionally based on the measuring signals. The compensation signals are received by the compensating thermopiles 28, which utilize the compensation signals to generate electric cooling or heating power to maintain the cells 12 at a generally constant temperature.
- This compensation is accomplished by Peltier heat produced by the compensating thermopile rather than by electric heaters, because the heat of mixing might be positive or negative.
- the amount of heating or cooling effectuated by the compensating thermopile is controlled by the computer 40, which accomplishes such control simply by regulating the magnitude and direction of current travelling to the compensation thermopile.
- the initial filling of the cell with the first reagent is accomplished via injection device 22 and tangential inlet tube 16.
- the first reagent sits in the cell waiting to be mixed with the second reagent, which is subsequently, rapidly introduced into the cell via injection device 20 and radial inlet tube 14.
- the second reagent is injected into cell 12 in a very rapid, short pulse (e.g, of 1-2 microliters) via injection device 20 and radial inlet tube 14, the first reagent initially in the cell is displaced very rapidly from the cell through the outlet tube 18 before any substantial mixing between the reagents can occur.
- the composition of the initial mixture within the cell can be very precisely estimated. This is in contrast with conventional, slow injection titration methods (i.e., with a time constant slower than the mixing time) which result in a continuously varying composition of the liquid that leaves the reaction cell.
- a predetermined additional amount of the first reagent (e.g., approximately 10-20 microliters) is injected into the cell 12 via injection device 22 and tangential inlet tube 16 to obtain complete and efficient turbulent stirring of reagents.
- this reduces the concentration of the second reagent within the cell 12, and this is taken into account by computer 40 when calculating the heat of reaction.
- the injection device 22 withdraws a predetermined amount of mixed solution from the cell via tangential inlet tube 16 and then reinjects this predetermined amount of solution back into the cell to cause a turbulent, circular stirring of mixed reagents within the cell.
- the magnitude of mechanical heat effects were evaluated by injecting 3 to 20 microliters of water into a single cell filled with water.
- the injection rate used was 80 microliters per second, which corresponds to a jet speed of 4.8 m/sec.
- the heat effect is very reproducible and ranges between 1.8 and 12.4 micro Joules, respectively.
- the heat effect of mechanical work at the time of injection was also evaluated by measuring the differential heat effect obtained upon the simultaneous injection of the same amount of water, 3 micro liters, in both cells of the dual microcalorimeter.
- This differential heat effect is much smaller than the effect of injection of water into one cell alone, i.e., the heat effect of injection in two cells are almost equal and compensate each other.
- the small difference between these effects is highly reproducible and can be easily decreased almost to zero by small adjustments in the speed and/or volume of jets in each of the cells.
- one of the calorimeter cells was filled with 0.5M GdmCl (volume 0.3 ml), and, at predetermined times, 5 micro-liters of water were injected.
- the reference cell was filled with water, and similar 5 micro-liter injections of water were made.
- the observed heat effect of injection i.e., the difference of the two Joule heats of mixing, was very small. It did not exceed 1% of the heat of mixing GdmC1 with water and could be easily taken into account in order to obtain the heat of reaction.
- FIG. 7 is a schematic representation of a differential titration calorimeter, in accordance with the principles of the present invention, wherein two different types of reactors are provided and share a common thermostated block 41. More specifically, for example, in FIG. 7 a jet-type calorimetric reactor 10 as described hereinbefore is provided as one reactor, while a conventional Flow-Mix calorimetric reactor 42 is provided as the other reactor. Using a combination of two functionally different cells with the same thermostated block eliminates the need for using a separate reference cell. That is, in this arrangement, each cell can be used as the reference cell of the other.
- the two inlet tubes 60 and 62 are both tangentially disposed with respect to the cell 64, and are removably inserted into an opening 66 in the rim 68.
- the outlet tube 70 is removably inserted into an opening 72 in the rim 68.
- the removability of the inlet tubes 60, 62 and outlet tube 70 lends flexibility to the assembly and facilitates cleaning of the cell 64 and tubes.
- the tubes 60 and 62 are preferably welded to one another and are inserted into the same hole 66 in the rim 68.
- FIG. 10 shows the instrument output in volts plotted over time in an experiment in which 5 micro-Joules of electrical calibration pulses were applied along with mixing pulses.
- FIG. 10 shows the baseline energy attributable to the heat effects of the mechanical mixing has been subtracted.
- FIG. 11 shows the measured energy of the pulses. The standard derivation for this experiment was 1.16 micro-Joules.
- FIG. 12 shows biochemical experimental results of titration of ribonuclease A (RNase) by cyclic monophosphate (2'CMP).
- the concentration of Rnase in the calorimetric cell was 1.01 ⁇ 10 -4 M, and the concentration of 2'CMP was 1.0 ⁇ 10 -3 M.
- the volume of the calorimetric cell was 0.438 mL, and the reagent 2'CMP was injected in 5 micro-liter portions.
- the cumulative heat of reagent binding by protein is shown in FIG. 13.
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US08/534,699 US5707149A (en) | 1995-09-27 | 1995-09-27 | Device and method for measuring the heat of reaction resulting from mixture of a plurality of reagents |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2002008710A1 (en) * | 2000-07-21 | 2002-01-31 | Point Of Care Ab | A micro-calorimeter apparatus |
US6402369B1 (en) * | 1998-11-03 | 2002-06-11 | Sarnoff Corporation | Arrayable thermal assays |
US6953280B2 (en) * | 2000-09-04 | 2005-10-11 | Eidgenössische Technische Hochschule Zürich | Calorimeter |
WO2007053105A1 (en) * | 2005-10-31 | 2007-05-10 | Senzime Point Of Care Ab | A biosensor apparatus for detection of thermal flow |
US20080112457A1 (en) * | 2004-07-16 | 2008-05-15 | Health Scientific Co. Ltd. | Calorimeter |
US20080273572A1 (en) * | 2006-06-02 | 2008-11-06 | James Madison University | Thermal detector for chemical or biological agents |
US20100296544A1 (en) * | 2007-12-19 | 2010-11-25 | Centro De Investigacion Y De Estudios Avanzados Del Instituto Politecnico Nacional | Scan adiabatic resistive calorimeter (sarc) with ohm heating in the sample |
US9593988B1 (en) | 2013-07-23 | 2017-03-14 | Calmetrix, Inc. | Systems and methods of thermal energy measurement |
CN106770457A (en) * | 2015-11-24 | 2017-05-31 | 神华集团有限责任公司 | A kind of pyrolysis of coal Reaction heat determination method based on heat flow flux type DSC technique |
WO2018220153A1 (en) * | 2017-06-02 | 2018-12-06 | Calbact Ag | Calorimeter |
CN112782224A (en) * | 2020-12-31 | 2021-05-11 | 西南科技大学 | Method and device for measuring combustion heat of material |
CN112782223A (en) * | 2020-12-31 | 2021-05-11 | 西南科技大学 | Calorimetric system of combustion heat tester |
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US5482679A (en) * | 1993-06-08 | 1996-01-09 | N.V. Nederlandse Gasunie | Device for determining the Wobbe index of a gas mixture |
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US3716333A (en) * | 1969-12-09 | 1973-02-13 | Kali Chemie Ag | Process of and apparatus for thermometric analysis |
US5482679A (en) * | 1993-06-08 | 1996-01-09 | N.V. Nederlandse Gasunie | Device for determining the Wobbe index of a gas mixture |
Cited By (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6402369B1 (en) * | 1998-11-03 | 2002-06-11 | Sarnoff Corporation | Arrayable thermal assays |
JP2002539419A (en) * | 1998-11-03 | 2002-11-19 | サーノフ コーポレーション | Alignable thermal assay |
WO2002008710A1 (en) * | 2000-07-21 | 2002-01-31 | Point Of Care Ab | A micro-calorimeter apparatus |
US20040028112A1 (en) * | 2000-07-21 | 2004-02-12 | Thomas Carlsson | Micro-calorimeter apparatus |
US8262989B2 (en) * | 2000-07-21 | 2012-09-11 | Senzime Ab (Publ.) | Micro-calorimeter apparatus |
US6953280B2 (en) * | 2000-09-04 | 2005-10-11 | Eidgenössische Technische Hochschule Zürich | Calorimeter |
US20080112457A1 (en) * | 2004-07-16 | 2008-05-15 | Health Scientific Co. Ltd. | Calorimeter |
US7947223B2 (en) | 2005-10-31 | 2011-05-24 | Senzime Ab | Biosensor apparatus for detection of thermal flow |
US20090098019A1 (en) * | 2005-10-31 | 2009-04-16 | Senzime Point Of Care Ab Genetikvagen 10A | Biosensor apparatus for detection of thermal flow |
WO2007053105A1 (en) * | 2005-10-31 | 2007-05-10 | Senzime Point Of Care Ab | A biosensor apparatus for detection of thermal flow |
US20080273572A1 (en) * | 2006-06-02 | 2008-11-06 | James Madison University | Thermal detector for chemical or biological agents |
US20100296544A1 (en) * | 2007-12-19 | 2010-11-25 | Centro De Investigacion Y De Estudios Avanzados Del Instituto Politecnico Nacional | Scan adiabatic resistive calorimeter (sarc) with ohm heating in the sample |
US8613545B2 (en) * | 2007-12-19 | 2013-12-24 | Centro De Investigación Y De Estudios Avanzados Del Instituto Politécnico Nacional | Scan adiabatic resistive calorimeter (SARC) with ohm heating in the sample |
US9593988B1 (en) | 2013-07-23 | 2017-03-14 | Calmetrix, Inc. | Systems and methods of thermal energy measurement |
CN106770457A (en) * | 2015-11-24 | 2017-05-31 | 神华集团有限责任公司 | A kind of pyrolysis of coal Reaction heat determination method based on heat flow flux type DSC technique |
CN106770457B (en) * | 2015-11-24 | 2019-06-21 | 神华集团有限责任公司 | A kind of pyrolysis of coal Reaction heat determination method based on heat flow flux type DSC technique |
WO2018220153A1 (en) * | 2017-06-02 | 2018-12-06 | Calbact Ag | Calorimeter |
CN110785641A (en) * | 2017-06-02 | 2020-02-11 | 卡尔巴科特公司 | Calorimeter with a heat measuring tube |
CN110785641B (en) * | 2017-06-02 | 2021-07-27 | 卡尔巴科特公司 | Calorimeter with a heat measuring tube |
US11639877B2 (en) * | 2017-06-02 | 2023-05-02 | Calbact Ag | Calorimeter with multiple heat sinks and an amplifier |
CN112782224A (en) * | 2020-12-31 | 2021-05-11 | 西南科技大学 | Method and device for measuring combustion heat of material |
CN112782223A (en) * | 2020-12-31 | 2021-05-11 | 西南科技大学 | Calorimetric system of combustion heat tester |
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